Theoretical study of the structures and stabilities of the carbon dioxide dimer ((CO2)2-) ions

Fleischman, Stephen H.; Jordan, Kenneth D.

doi:10.1021/j100290a006

Cited by 96 publications

(87 citation statements)

References 2 publications

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“…3 Since cluster reactivity 25 and dynamics are largely determined by the ionic core, a fundamental question regarding all three of the above cluster families is whether the excess electron is localized on a single monomer or shared between two ͑or more͒ monomer moieties. 1,13,14,[17][18][19][20]23,24 The charge localization or sharing lead to different electronic and structural isomers, which have been observed for (CO 2 ) n Ϫ and (CS 2 ) n Ϫ , 18,19,22 and hypothesized for (OCS) n Ϫ . 3 For example, the (CO 2 ) n Ϫ photoelectron spectra reveal discontinuities in the dependence of the vertical detachment energy ͑VDE͒ on cluster size.…”

Section: Introductionmentioning

confidence: 99%

“…3 While the isovalent (CO 2 ) n Ϫ and (CS 2 ) n Ϫ clusters have been the subject of many experimental 4 -22 and theoretical 17,20,21,23,24 studies, only one previous experiment investigated the interaction of (OCS) n Ϫ with light. 3 Since cluster reactivity 25 and dynamics are largely determined by the ionic core, a fundamental question regarding all three of the above cluster families is whether the excess electron is localized on a single monomer or shared between two ͑or more͒ monomer moieties.…”

Section: Introductionmentioning

confidence: 99%

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Photoelectron imaging of carbonyl sulfide cluster anions: Isomer coexistence and competition of excited-state decay mechanisms

Surber

Sanov

2003

The Journal of Chemical Physics

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Articles you may be interested inVibrationally resolved photoelectron imaging of platinum carbonyl anion Pt(CO) n − (n = 1-3): Experiment and theory J. Chem. Phys. 137, 204302 (2012); 10.1063/1.4768004 Thermal effects on energetics and dynamics in water cluster anions (H2O) n − J. Chem. Phys. 136, 094304 (2012); 10.1063/1.3689439 Photoelectron spectroscopy of pyrene anion clusters: Autodetachment via excited states of anion and intermolecular interactions in anion clustersProbing isomer interconversion in anionic water clusters using an Ar-mediated pump-probe approach: Combining vibrational predissociation and velocity-map photoelectron imaging spectroscopies

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photoelectron imaging of carbonyl sulfide cluster anions: Isomer coexistence and competition of excited-state decay mechanisms

Surber

Sanov

2003

The Journal of Chemical Physics

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“…46 -57 CO 2 dimer anions first detected experimentally 46,47 have since been studied by theory. 48,49 It appears that two isomers play a role: CO 2 Ϫ •CO 2 with C s symmetry and oxalate O 2 CvCO 2 Ϫ , with D 2d symmetry, the latter being more stable. Photoelectron spectra suggest that as additional CO 2 molecules are added, the relative stability of the two isomeric forms of the ionic core may change first from favoring D 2d to C s at Nϭ6 and back to D 2d at Nϭ14 and that these core-switching events may explain observed magic numbers below Nϭ15.…”

Section: Introductionmentioning

confidence: 99%

Electron attachment time-of-flight mass spectrometry reveals geometrical shell closings in van der Waals aggregates

Ingólfsson¹,

Wodtke²

2002

The Journal of Chemical Physics

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Articles you may be interested inPhotodissociation of (SO2XH) Van der Waals complexes and clusters (XH = C2H2, C2H4, C2H6) excited at 32 040-32090 cm−1 with formation of HSO2 and X J. Chem. Phys. 140, 054304 (2014); 10.1063/1.4863445Infrared absorption of methanethiol clusters (CH3SH) n , n = 2-5, recorded with a time-of-flight mass spectrometer using IR depletion and VUV ionization A new method to study metastable fragmentation of clusters using a reflectron time-of-flight mass spectrometer Rev.Using electron attachment time-of-flight mass spectrometry, we show how high-precision structural constants of van der Waals aggregates may be obtained for two kinds of homogeneous clusters, (SF 6 ) N and (CO 2 ) N . Furthermore, we obtain size-specific structural information over a wide range of aggregate sizes. Mass spectrometric data are presented regarding the size needed to facilitate the transition from ''cluster packing,'' dominated by nearest-neighbor interactions, to bulk-like packing.For both examples, it appears that the cluster-to-bulk packing transition may occur even for aggregates where the majority of the molecules resides at the surface. The critical size for the cluster-to-bulk transition may be related to the size at which molecules packed as bulk crystals can begin forming nearly spherical shapes. A discussion of the mechanism by which geometrical shell closings are visualized in electron attachment time-of-flight mass spectrometry is also presented. We postulate that these observations reflect the dynamics of electron localization in ordered crystallites with and without defects.

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“…Let us first discuss the properties of the smallest 'cluster' anion, the dimer. Early ab initio work at Hartree-Fock (HF) [102,103] and post-HF levels by Jordan and coworkers [98] identified two structural motifs for (CO 2 ) À 2 (see Figure 5). In the 'monomer anion' motif, the charge is mostly localised on a single CO 2 molecule, while Figure 5.…”

Section: 2mentioning

confidence: 99%

“…The 'monomer' (left) and 'dimer' (right) structural motifs for the (CO 2 ) À 2 anion. Note that there are additional conformers of the 'monomer' motif with C s symmetry [98][99][100]. Reprinted with permission from [101].…”

Section: 2mentioning

confidence: 99%

The interaction of negative charge with carbon dioxide – insight into solvation, speciation and reductive activation from cluster studies

Weber

2014

International Reviews in Physical Chemistry

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The interaction of CO 2 with negative charge is of high importance in many natural and industrial processes, since reductive activation is one of the most common and convenient ways to chemically unlock this robust molecule. While free CO 2 does not form stable anions, the accessibility of low-lying molecular orbitals is critical for its chemical versatility and allows CO 2 to act as solvent as well as a reaction partner for negative ions. Experiments on mass selected cluster ions are highly suitable for the study of the fundamental properties of CO 2 and its interaction with excess electrons and anions, since they circumvent many problems associated with experiments in the condensed phase. The combination of mass spectrometry, laser spectroscopy and quantum chemical calculations results in a powerful tool set to address questions of reactivity, ion speciation and solvation, and they can provide key information to understanding the ion chemistry of CO 2 .

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Theoretical study of the structures and stabilities of the carbon dioxide dimer ((CO2)2-) ions

Cited by 96 publications

References 2 publications

Photoelectron imaging of carbonyl sulfide cluster anions: Isomer coexistence and competition of excited-state decay mechanisms

Photoelectron imaging of carbonyl sulfide cluster anions: Isomer coexistence and competition of excited-state decay mechanisms

Electron attachment time-of-flight mass spectrometry reveals geometrical shell closings in van der Waals aggregates

The interaction of negative charge with carbon dioxide – insight into solvation, speciation and reductive activation from cluster studies

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